Styrene

proprietary process technology

Piazza Boldrini, 1
20097 San Donato Milanese (MI)
Tel. +39 02 520.1
info@versalis.eni.com

Licensing
Piazza Boldrini, 1
20097 San Donato Milanese (MI)
Tel. +39 02 520.32992
Fax +39 02 520.42361
info.licensing@versalis.eni.com
proprietary process technologies versalis proprietary process technologies introduction to versalis
phenol and derivatives
Cumene (with PBE-1 zeolite based proprietary catalyst) * available for licensing styrene technology
Phenol, Acetone, Alphamethylstyrene *
High selectivity Cyclohexanone
Acetone hydrogenation to Isopropyl Alcohol * our company versalis is in the position to offer a competitive styrene technology which has been
Isopropyl Alcohol to Cumene * versalis – the petrochemical subsidiary of eni – is a dynamic player in its industry developed by taking great advantages of versalis long experience in both plant
Ammoximation
(with Titanium silicalite based proprietary catalyst TS-1) sector facing the multifold market needs through different skills. design and styrene manufacturing and sales. As in the present competitive styrene
market even small differences in raw materials and utilities specific consumption
DMC and derivatives
Dimethylcarbonate With a history as European manufacturer with more than 50 years of operating can heavily influence the profit, the technology can be furthermore really tailored
(via Carbon Monoxide and Methanol) * experience, versalis stands as a complete, reliable and now global supplier in the and customized to site conditions and customer needs.
Diphenylcarbonate *
basic chemicals, intermediates, plastics and elastomers market with a widespread Styrene technology is reliable and proven at industrial scale, with the first plant
polyethylene sales network. come on stream in the early nineties and another plant with a 600 KTA capacity
LDPE
EVA successfully started-up in early 2010.
Relying on continuous development in its production plants as well as in its products,
styrenics
Ethylbenzene strengthening the management of the knowledge gained through its long industrial Key features of versalis styrene production technology are:
(with PBE-1 and PBE-2 zeolite based proprietary catalyst) experience, versalis has become a worldwide licensor of its proprietary technologies • low ethylbenzene consumption;
Styrene
GPPS and proprietary catalysts. The strong integration between R&D, Technology and • high conversion/yield;
HIPS Engineering departments, as well as a deep market expertise, are the keys strength • high styrene quality;
EPS suspension polymerization
EPS continuous mass polymerization for finding answers to customers requirements. • low energy consumption (high level of heat recovery);
ABS continuous mass polymerization • unique and patented solutions for EB/steam mixing and reactor effluents main
SAN
Our commitment to excellence, in quality of our products and services, makes our condenser;
elastomers company an active partner for the growth of customers involved in petrochemical • long catalyst life;
emulsion-SBR
solution-SBR business. • high plant reliability (due to thermal and mechanical analysis during design);
SBS • optimized hot zone lay out (position of reactors and exchangers are settled
SIS
LCBR Through engineering services, technical assistance, marketing support and in order to minimize residence time at high temperature in interconnecting
HCBR continuous innovation, our knowledge is the key strength to customize any new pipelines, taking care either of pressure drop and piping elasticity);
NBR
Carboxylated latices project throughout all phases. • low maintenance cost;
EP(D)M • versalis can also offer proprietary technologies which can be considered as
proprietary catalysts Customers can rely on this strong service-oriented outlook and benefit from a option for a better integration of the styrene unit with site condition;
Titanium silicalite product portfolio that strikes a perfect balance of processability and mechanical • proprietary technology for the up-grade of hydrogen off-gas to be used as raw
PBE-1 Zeolite
PBE-2 Zeolite properties, performance and eco-friendliness. material in hydrogenation process;
• proprietary technology for PA (phenyl acetylene) reduction;
* Co-licensing in cooperation with Lummus Technology
• proprietary technology for benzene by-product treatment for its recycle to a
liquid phase zeolite EB process.
 product quality
Styrenje (dry)
main process parameters
Ethylbenzene consumption
(MT per MT styrene)
Continuous run length
EB conversion per pass
versalis can always provide appropriate solutions to different client’s needs thanks
99.95% wt to its capabilities and experience in the following fields:
research & operation
versalis background and expertise in Styrene technology comes both from
manufacturing experience and the presence of a strong R&D team established in
1.051 Mantova since the early 70s. A great and updated know how comes from continuous
lab & pilot plant testing on dehydrogenation catalysts and polymerisation inhibitors/
up to 36 months retarders to be then applied on Styrene industrial plants.
A simulation program, suitable to optimise inhibitor/retarder dosage against
up to 71% polymer formation prediction, has been developed and applied since many years.
process design
process design is flexible and able to face different conditions and constrains.
Any project is individually evaluated to offer the best solution, tailored to specific
customers needs. Thermal and fluodynamic analysis (CFD) are applied to hot area
reactors/exchangers and interconnecting piping to increase heat recovery, minimise
pressure drop and reduce lack of homogeneity in distribution.
The great attention to minimise hot void volume, where low selectivity reactions
take place, and the run of the reaction at very low pressure, has led to an improved
design able to maximise catalyst performances and overall process selectivity.
wastes and emissions
The process produces oily waste water which can be treated in a normal
bio-treatment.
As a option, a special treatment can be included in the plant in order to recover such
liquid effluent as boiler feed water.
Other liquid waste and continuous / non-continuous vents can be sent to the
steam super-heater furnace in order to lower all the plant emissions to a practically
negligible amount.
Spent catalyst at the end of its lifetime can be disposed in a normal landfill.
industrial applications
Two styrene plants, based on proprietary technology, are on stream in Italy: a
430 kt/y, 2 reaction stages and a 190 kt/y, 3 reaction stages.
A styrene unit of 600 kt/y has been licensed by versalis and started-up in
early 2010.

mechanical design
versalis Engineering Dept. has been working in close coordination with the Process
Dept. since a long time. This fact has allowed to develop unique and well sound
engineering solutions for critical equipments, that guarantee the best results in
terms of mechanical reliability and process performances.
Thermal and mechanical analysis (including FEA) are applied to minimise
temperature gradients, reach smooth discontinuity in wall thickness, improve stress
distribution.
 process description Styrene • process scheme
reaction (hot Zone):
the gas phase ethylbenzene dehydrogenation occurs in two or three reactors used
in series with interstage re-heater. The heat is provided by superheated steam, which,
Steam hydrogen
at the end of the cycle, will enter in the first reactor together with ethylbenzene.
The main reaction by-products are toluene and benzene; hydrogen rich off-gas
is normally recycled in the steam superheater as fuel gas. Due to high operative
temperature a small amount of heavy components are formed. Off gas recovery

condensation (cold Zone):

the reaction effluent, after heat recovery, is sent to the following section, where
organic and steam are condensed and separated from off gases (hydrogen, carbon Steam superheater
dioxide, methane, ethylene, etc).
Dehydrogenation
Off gas is removed by a compressor that assures the sub-atmospheric pressure in
reactors
the reactors. Water is purified and normally reused, whereas organic phase is sent Heat recovery
Ethylbenzene from EB plant System Condenser
to distillation section. With reference to such scheme, versalis can offer different
process solutions, in order to best fit customer need.
distillation:
crude styrene (about 70%) with ethylbenzene, benzene, toluene and some heavy
components, is fed to the first column where benzene and toluene are recovered as
overhead. Such mixture can be fed to another column where benzene and toluene
are separated. Ethylbenzene, styrene and heavies feed another column, where Benzene
ethylbenzene is separated from styrene in vacuum conditions. The bottom is fed to
the following column, where pure styrene is recovered from the top. The bottom is BZ/TOR splitter
SM product EB recycle Optional
further processed in a finishing equipment, to recover additional styrene from the
residue. In the overhead vapour of the styrene column p-tert-butylcatechol (TBC) is Dehydrogenated Steam
added, to prevent the polymerisation of styrene in the storage. mixture Condensate
Although distillation columns work in vacuum, bottoms temperatures can vary Toluene by-product
from 85 to 110 °C. For this reason it is necessary to add an inhibitor to avoid losses
of styrene due to polymerisation. Different substances as inhibitors or retarders
SM TAR SM column EB/SM column BZ/TOL column
can be used for this purpose as nitroderivatives, free radicals, etc; they can be used
alone or in combination, to have a possible synergetic effect. versalis can provide an
up-to-date design including special arrangements suitable to achieve low material
losses and energy consumption with very low inhibitor consumption. A wide range
of inhibitors and retarders have been tested and can be proposed.